Formulation And Method For Providing Safe, Clean Chlorinated Recreational Water

ABSTRACT

A solid formulation for use with sodium chloride and a chlorine generator to provide safe, clean chlorinated recreational water. The formulation comprises a chlorine stabilizing agent and a phosphate remover agent. An enhanced salt comprising a chlorine stabilizing agent, a phosphate remover agent and sodium chloride is also described. The formulation and enhanced salt can also contain a metal chelating agent and a pH balancing agent. A cleaning agent may also be included. A fast dissolving sodium cyanurate compound is used for the chlorine stabilizing agent. A method, kit, and system for providing safe, clean chlorinated recreational water are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.11/806,980 filed Jun. 5, 2007 (U.S. Pat. No. 7,462,296; Issue Date: Dec.9, 2008), which is a continuation of U.S. patent application Ser. No.10/937,263 filed Sep. 10, 2004 (U.S. Pat. No. 7,238,287; Issue Date:Jul. 3, 2007).

BACKGROUND

1. Field of the Invention

The invention relates to water sanitation and maintenance.

2. State of the Art

Swimming pools and other bodies of recreational water provide a sourceof entertainment for people all over the world. Whether used to cool offon a hot summer day or to swim laps for exercise, swimming pools are animportant part of our culture. They offer a safe and clean environmentfor people, especially children, to enjoy the water even in landlocked,dry locations.

Although swimming pools have many positive characteristics, they canalso be breeding grounds for bacteria and other living organismsincluding disease-causing microbes. Thus, in order to provide safe,sanitary, and aesthetically pleasing water, proper swimming poolmaintenance must be undertaken.

The key factors in maintaining recreational water are disinfection,sanitation, oxidation, water balance, filtration, and circulation.Sanitation kills undesired living organisms in the water. Disinfectioncontrols disease-causing microbes. Oxidation oxidizes organic andsynthetic contaminants to benign forms. Water balance refers to the pH,alkalinity, and calcium water hardness. Filtration removes deadorganisms and oxidized debris from the water. Circulation works withfiltration to provide clean chemically treated water to all areas of thepool.

The most common agent for oxidation and sanitation is chlorine. Whenchlorine gas, Cl₂, dissolves in water, it hydrolyzes according to thereaction:

Cl_(2(g))+H₂O₍₁₎→HOCl_((aq))+HCl_((aq))

The chlorine of the hydrochloric acid does not contribute to thesanitation. It is the hypochlorous acid, HOCl which actually kills themicrobial bodies. The bactericidal power of hypochlorous acid isattributed to its ability to defuse through cell walls and reach thevital parts of the bacteria cells. Hypochlorous acid, being a weak acid,ionizes in water according to the reaction:

HOCl_((aq))

H⁺ _((aq))+OCl⁻ _((aq))

According to Le Chatelier's Principle, this reversible reaction willmove towards equilibrium when subjected to an external change. Thus, ifa product is added to the system, the reaction will shift to the leftand more reactant will form. If the amount of product is reduced, thereaction will shift to the right and more product will form. Thus, ifthe ph of the water is lowered, making the water more acidic and raisingthe h⁺ ion concentration; the equilibrium is forced to the left and morehypochlorous acid is present. Conversely, if the ph of the water israised, the h⁺ ion concentration is lowered and the reaction is forcedto the right; forming more ocl⁻ ion. Consequently, any free chlorine orhypochlorite added to water will immediately distribute itself into hodand ocl⁻ with the ratio for the two being controlled primarily by the phvalue of the water.

As a bactericide, chlorine kills unwanted organisms in water includingalgae and is non-toxic to humans in low concentration. Traditionally,solid chlorine tablets, liquids, and various dry compounds of chlorinehave been added to pool water to maintain the recommended concentration.However, this requires daily maintenance and is very time consuming.

Due to recent improvements in process control, chlorine generators havebecome a popular tool in pool management. Chlorine generators, alsoknown as salt generators, electrolytically produce pure chlorine gasform chlorine salts added to the water. Commonly, table salt or sodiumchloride is used as the chlorine source for these generators. For theoxidation and sanitation steps, one simply adds an amount of sodiumchloride based on the size of the pool.

Chlorine generators thus offer residential and commercial pool ownersand managers a safe convenient way for maintaining the proper chlorineconcentration in their pools. However, problems may be encountered whenusing chlorine generators. For example, it may be difficult to maintainthe recommended free chlorine concentration even though the correctamount of sodium chloride was used. This is due to the free chlorinebeing degraded by sunlight. Ultraviolet radiation from the sun greatlydepletes free chlorine in a short period of time. To reduce thisdepletion, a stabilizing agent or so-called conditioner is commonlyadded to the pool water. Cyanuric acid is by far the most commonly usedstabilizing agent. This chemical assists in keeping the sanitizer in thewater by preventing or slowing down the ultraviolet degradation ofchlorine. The ideal concentration of cyanuric acid in the water isbetween 30 to 50 ppm or parts per million. Present in thisconcentration, cyanuric acid will keep chlorine in water 8-10 timeslonger than in water with no cyanuric acid. Without cyanuric acid,chlorine loss is 90 percent in just 2 hours. However, cyanuric acid isaccompanied with its own issues. It is an acid so it will lower the pHof the water. It is also very slow dissolving. It can take from 4 to 7days to dissolve in a pool depending on circulation, water balance, andwater temperature. If non-dissolved cyanuric acid is left in contactwith the pool vessel surface for a prolonged period of time, it can etchplaster, degrade or stretch vinyl liners, and corrode metals which canstain the swimming pool vessel surface. Further, if cyanuric acid isadded through a pool's surface skimmer, as is commonly done,non-dissolved cyanuric acid can harm the metal components in the pool'splumbing and filtration system.

There are also problems encountered relating to fouling of theelectrolytic plates in chlorine generators. Fouling refers to chemicalbuildup on the plates. The electrolytic plates are subject to shortenedlife spans if suntan oil, grease, soap scum, or other hydrocarbon-basedsynthetic personal care chemicals coat or foul the plates. Theefficiency of chlorine generators are reduced if the plates becomedirty. The use of an enzyme based product added to the water will helpprevent the plates from getting fouled. Regular use of an enzyme in thewater will also help reduce the amount of grease and oil present in thepool water.

Chlorine generator plates can also be fouled by calcium and magnesiumprecipitates building up on the plates. The most common buildup iscalcium carbonate or so-called scale. Extreme scale buildup can bridgethe distance between plates. This can cause either a short circuit or aburned area on the plate. The addition of ethylenediaminetetraaceticacid, or EDTA, is one common way of controlling scale. EDTA's mainfunction is to prevent stains by chelating metal ions. When filling apool for the first time or whenever a significant amount of water isadded there is a risk of metallic stains. Thus, a chelating agent iscommonly added while filling or soon after filling to prevent staining.

There are several other factors crucial to maintaining a safe, cleanpool. For example, not only is the concentration of chlorine importantfor effective disinfection but also the efficacy of the chlorine. Algaegreatly reduce the efficiency of chlorine in combating disease causingmicrobes. With algae present, the free chlorine is tied up fighting thealgae and its effectiveness against other organisms is reduced.Orthophosphates are the limiting nutrient for algae growth. Allphosphates in the water can degrade into orthophosphates. Thus, byreducing the phosphate concentration, the amount of algae that iscapable of growing is reduced. Ideally, the phosphate concentration iskept below 100 parts per billion or ppb and most preferably kept below50 ppb. At this concentration, only a small amount of algae is able togrow. To kill such a small population of algae, only a small amount ofchlorine is needed. Thus, the remaining chlorine is free to combat otherundesired organisms and the overall efficacy of the free chlorine israised. To this end, phosphate removers are commonly added torecreational water. Phosphate removers typically include lanthanum saltsand cause phosphates to precipitate out allowing them to be easilyremoved by filtration or vacuuming. For example, PHOSfree® of NaturalChemistry, Inc. utilizes lanthanum sulfate.

As discussed above, water balance, and especially the pH of the water,is another important factor in determining the efficacy of the freechlorine. When chlorine is added to water it forms HOCl (hypochlorousacid) which then dissociates into OCT⁻ (hypochlorite ion). HOCl is avery powerful killing form of chlorine in water. OCT⁻ is a rather weakdisinfectant and is about 80 times less effective than HOCl. Thepercentage of each of these forms is determined by the pH of the water.At a pH of about 7.5, there is about 55 percent of the chlorine in theHOCl form and about 45 percent in the OCl⁻ form. At a pH of about 8.0,there is about 28 percent in the HOCl form and about 72 percent in theweaker OCl⁻ form. Therefore keeping the pH in the proper range rendersthe chlorine more powerful and efficient. In order to maintain the pHwithin the desired range, pH buffers are commonly added to the water.

Maintaining the proper balance between all these chemicals is no easytask for pool owners and managers. Pool owners and managers constantlyover or under dose pool chemicals because most doses are calculated inppm or mg/L (milligrams per liter) both of which are a weight-to-weightexpression and they commonly use measuring cups, to measure out thechemicals, which is a volume measurement. Because of differentdensities, one cup of a dry chemical is not always 8 oz. dry weight.Other pool owners and managers simply guess at the weight based on aproportion of the container it is in. For instance, ⅕^(th) of a 5-poundcontainer is about one pound.

Further, even adding the correct sodium chloride is not always an easytask. Because salt is a commodity and cheap, many pool dealers do notsell it in their stores. Many dealers send customers to home andbuilding supply chains. Thus, there is a chance that the customer willbuy the wrong kind of salt. For example, salt can be purchased withhardening agents (e.g. sodium hexametaphosphate or SHMP), cleansers(e.g. citric acid based), free-flowing/anti-caking agents (e.g. YellowPrussiate of Soda or YPS), iron removal agents, detergents, andsurfactants. While not dangerous, adding the wrong salt could reduce thelife of the chlorine generator. It may also cause some staining anddiscoloration of the pool vessel.

In view of all the variables in maintaining safe clean swimming poolwater, there is a need for simplifying pool management. Specifically,there is a need for reducing the number of steps required to effectivelymaintain the water in swimming pools chlorinated with chlorinegenerators.

SUMMARY

One embodiment of the present invention comprises a solid formulation ofa stabilizing agent and a phosphate removing agent that can be easilyadded to a body of recreational water equipped with a chlorinegenerator. The formulation may further contain a metal chelating agentand a pH balancing agent. Optionally, a cleaning agent may also beincluded. The amount of each component within the formulationcorresponds to a specific amount of water. A user simply adds thecorrect amount of the formulation and the correct amount of sodiumchloride to the water and the chlorine generator provides safe, cleanchlorinated water.

Another embodiment of the invention comprises a solid formulationcomprising a stabilizing agent, a phosphate remover agent, a metalchelating agent, a pH balancing agent, and sodium chloride. Theformulation may further contain a cleaning agent. The formulation can beadded to a body of recreational water equipped with a chlorinegenerator. A user simply adds the formulation in the prescribed amountfor the size of the body of water and the chlorine generator providessafe, clean chlorinated water.

Another embodiment of the present invention comprises a method fortreating a body of water. The method comprises adding a solidformulation comprising a chlorine stabilizing agent, a phosphate removeragent, a metal chelating agent, a pH balancing agent, and sodiumchloride to the body of water; and electrolytically converting thesodium chloride into free chlorine. The formulation that is added mayfurther contain a cleaning agent. The method provides safe, cleanchlorinated water.

Another embodiment of the invention comprises a kit for maintaining abody of recreational water. The kit includes a container holding a solidformulation made up of a stabilizing agent, a phosphate remover agent, ametal chelating agent, a pH balancing agent, and sodium chloride; andinstructions for adding an effective amount of the formulation based onthe size of the body of water. The formulation included in the kit mayfurther contain a cleaning agent. A user simply adds the formulation inthe prescribed amount for the size of the body of water and incombination with a chlorine generator, safe, clean chlorinated water isprovided. The kit may also include testing strips for monthly testing ofthe water to ensure proper water chemistry is maintained.

Another embodiment of the invention comprises a system for maintaining abody of recreational water. The system includes a container holding asolid formulation made up of a stabilizing agent, a phosphate removeragent, a metal chelating agent, a pH balancing agent, and sodiumchloride; instructions for adding an effective amount of the formulationbased on the size of the body of water; and a chlorine generator. Theformulation may further contain a cleaning agent. A user simply adds thesolid formulation in the prescribed amount and the system provides safe,clean chlorinated water.

DESCRIPTION

One embodiment of the formulation of the present invention comprises achlorine stabilizing agent, a phosphate remover agent, a metal chelatingagent, and a pH balancing agent. The formulation may further contain asmall amount of sodium chloride. The formulation may also contain acleaning agent. The sodium chloride acts as a buffer between the otherchemicals. The formulation is solid and can be distributed in a smallpackage.

The chlorine stabilizing agent may be a salt of cyanuric acid. Thechorine stabilizing agent is preferably a non-chlorinated salt ofcyanuric acid. The chlorine stabilizing agent is more preferably amixture of mono-sodium, di-sodium, and tri-sodium cyanurate monohydrate.Most preferably, the mixture is highest in concentration in mono-sodiumcyanurate monohydrate. The mono form has a lower pH compared to theother forms. This stabilizer is an improvement over the forms ofcyanuric acid that are typically added to pool water. As detailed above,these forms of cyanuric acid are very slow dissolving and non-dissolvedcyanuric acid can lead to significant problems including damage to thepool vessel surface. The cyanurate compounds used in this invention arefast dissolving and as such are not encumbered by these issues. Thephosphate remover agent may comprise a partially soluble lanthanidecompound. Preferably, the phosphate remover agent comprises lanthanumsulfate. The metal chelating agent is preferably EDTA. The optionalcleaning agent is preferably enzyme containing.

The formulation may be pre-packaged in a convenient amount for aparticular volume of water. For instance, a small bag could be used totreat 5,000 gallons of water. A user simply adds the required number ofbags; say four bags for a 20,000 gallon pool. The user then adds therecommended amount of sodium chloride for use with a chlorine generatorfor the given pool and the chlorine generator provides safe, cleanchlorinated water. Thus, the present invention greatly simplifies pooltreatment management.

Another embodiment of the present invention includes an enhanced saltwherein sodium chloride is mixed in with a chlorine stabilizing agent, aphosphate remover agent, a metal chelating agent, and a pH balancingagent. The enhanced salt may also contain a cleaning agent. Thisembodiment of the formulation can be used directly with a chlorinegenerator. Thus, a user simply adds the formulation in an amount equalto the recommended amount of sodium chloride for the chlorine generatorfor the size of the pool and the chlorine generator provides safe, cleanchlorinated water.

Another embodiment of the present invention comprises a method fortreating recreational water. The method comprises adding the enhancedsalt to the recreational water; and electrolytically converting thesodium chloride in the enhanced salt into free chlorine. With thismethod, the enhanced salt only has to be added once per month tomaintain safe, clean chlorinated water.

Another embodiment of the invention comprises a kit for maintaining abody of recreational water. The kit includes a container holding ameasured amount of the enhanced salt and instructions for adding aneffective amount of the formulation based on the size of the body ofwater. A user simply adds the formulation in the prescribed amount forthe size of the body of water and in conjunction with a chlorinegenerator; safe, clean chlorinated water is provided. The kit can alsoinclude test strips along with instructions for monthly testing toensure all the chemicals are present in their desired concentrations.

Another embodiment of the invention comprises a system for maintaining abody of recreational water. The system includes a container holding ameasured amount of the enhanced salt, instructions for adding aneffective amount of the enhanced salt based on the size of the body ofwater, and a chlorine generator. A user simply adds the effective amountof the enhanced salt and the system provides safe, clean chlorinatedwater.

The formulation is formed by mixing together each solid component in theprescribed amount for a specific volume of water. For example, aspecific amount of phosphate remover agent is used for a specific amountof water to provide the water with a phosphate concentration of lessthan 50 parts per billion. Specifically, a formulation to treat 5000gallons of water comprises 22.5 g of lanthanum sulfate, 1.158 kg of amixture of mono-, bi-, and tri-sodium cyanurate, and 377 g of EDTA. For5000 gallons of water, 60.78 kg of sodium chloride are used. Theseamounts are based on fill water containing around 300 ppborthophosphates which is typical. However, in different locations andunder different circumstances, fill water with different concentrationsof orthophosphates and other compounds could be encountered. For thesesituations, the formulation could contain different amounts of thechemicals or supplemental amounts of each or certain chemicals could beincluded in the kit. The amounts of other chemicals such as ph balancingagents and optional enzyme-based cleaning agents required for a specificvolume of water are well-known and as such are not included here.

The optional solid enzyme-based cleaning agent can be formed by freezedrying liquid enzyme that is commonly used in pool maintenance. Freezedrying as opposed to flash drying or evaporating will not negativelyaffect the activity of the enzymes.

The several embodiments of the present invention greatly improve theefficiency of chlorine generators. By combining the treatment chemicalswithin a single formulation, it is ensured that the interrelatedchemicals are present in the recommended amount. The cyanuric acidconcentration is maintained at between 30 and 50 ppm such that thedepletion of free chlorine due to ultraviolet radiation is greatlyreduced. Also the mixture of mono-, bi-, and tri-sodium cyanuratemonohydrate is fast dissolving and will not cause the significantproblems associated with the slow dissolving forms of cyanuric acid thatare typically used as a stabilizing agents. The phosphate remover agentis present in a concentration such that the phosphate concentration ismaintained below 100 ppb and most preferably below 50 ppb. This isimportant because phosphates are the limiting nutrient for algae growth.Thus, very little algae is capable of growing in such an environment andthe small amount of algae that is able to grow is easily killed by asmall amount of chlorine. Since only a small amount of chlorine isneeded to control the algae, there is a large amount of remainingchlorine to combat other unwanted organisms. The pH balancing agentmaintains the pH within a safe range and a range such that a greaterpercentage of the chlorine is in the HOCl form thus increasing theefficiency of the chlorine as an oxidation agent. The metal chelatingagent reduces stain formation and reduces scale buildup and fouling ofthe electrolytic plates of the chlorine generator, thus increasing theefficiency of the chlorine generator. EDTA is preferred over other metalchelating agents because it does not contain any compounds thatbreakdown into orthophosphates upon dissociation in water. Thus, thephosphate concentration is not increased by the addition of the EDTA,keeping the algae population low, and not decreasing the effectivenessof the chlorine. The optional cleaning agent keeps the plates clean thusreducing the resistance between the plates and increasing the efficiencyof the chlorine generator. Enzymes are a preferred cleaning agentbecause they also break down organisms further taking the load off thechlorine and increasing its efficiency.

The several embodiments of the present invention greatly simplify poolmaintenance for pool owners and managers. Pools are an important sourceof leisure and exercise and can significantly increase the value of ahome but as detailed above they can also require a large amount of work.With the current invention, the time required for water maintenance isgreatly reduced and the pool's real value can be realized. For example,conventionally chemicals must be added to pool water at least once perweek. With the several embodiments of the present invention, one wouldonly have to add the formulation once per month.

Although particular embodiments of this invention have been disclosedherein for purposes of explanation, further modifications or variationsthereof will be apparent to those skilled in the art to which thisinvention pertains. For example, other additives could be included inthe formulation including compounds commonly used in swimming pool watermaintenance. The formulations could also contain fewer components ifdesired. For example, if a new pool already contains a sufficient amountof metal chelating agent it may be desirable to omit the EDTA from theformulation. Other components can be omitted for similar reasons. Thus,the scope of the present invention is only limited by the appendedclaims.

1. A solid formulation for providing safe, clean chlorinatedrecreational water, said formulation comprising: (a) a chlorinestabilizing agent; (b) a phosphate remover agent.
 2. The formulation ofclaim 1, wherein the chlorine stabilizing agent comprises a solidcyanuric acid salt.
 3. The formulation of claim 2, wherein the chlorinestabilizing agent comprises a solid non-chlorinated cyanuric acid salt.4. The formulation of claim 3, wherein the chlorine stabilizing agentcomprises a mixture of mono-sodium cyanurate monohydrate, di-sodiumcyanurate monohydrate, and tri-sodium cyanurate monohydrate.
 5. Theformulation of claim 1, wherein the phosphate remover agent comprises alanthanide compound.
 6. The formulation of claim 1, wherein theformulation further comprises a metal chelating agent.
 7. Theformulation of claim 1, wherein the formulation further comprises a pHbalancing agent.
 8. The formulation of claim 1, further comprising anenzyme-based cleaning agent.
 9. A method for providing chlorinated waterfor recreational purposes by adding: (a) a chlorine stabilizing agent;and (b) a phosphate remover agent to a body of recreational waterequipped with a chlorine generator.
 10. The method of claim 9, whereinthe chlorine stabilizing agent comprises a solid cyanuric acid salt. 11.The method of claim 9, wherein the chlorine stabilizing agent comprisesa solid non-chlorinated cyanuric acid salt.
 12. The formulation of claim9, wherein the chlorine stabilizing agent comprises a mixture ofmono-sodium cyanurate monohydrate, di-sodium cyanurate monohydrate, andtri-sodium cyanurate monohydrate.
 13. The method of claim 9, wherein thephosphate remover agent comprises a lanthanide compound.
 15. The methodof claim 9, wherein the formulation further comprises a metal chelatingagent.
 16. A solid formulation for use with a chlorine generator toprovide safe, clean chlorinated recreational water, said solidformulation comprising: (a) a chlorine stabilizing agent; (b) aphosphate remover agent; (c) a metal chelating agent; and (d) a pHbalancing agent.
 17. The formulation of claim 16, wherein the chlorinestabilizing agent comprises a solid cyanuric acid salt.
 18. Theformulation of claim 17, wherein the chlorine stabilizing agentcomprises a solid non-chlorinated cyanuric acid salt.
 19. Theformulation of claim 16, wherein the chlorine stabilizing agentcomprises a mixture of mono-sodium cyanurate monohydrate, di-sodiumcyanurate monohydrate, and tri-sodium cyanurate monohydrate.
 20. Theformulation of claim 16, wherein the phosphate remover agent comprises alanthanide compound.